Mixture of fungicidal agents

ABSTRACT

A fungicidal composition comprising a fungicidally effective amount of compound I selected from the group consisting of ##STR1## and an approximately equal weight of compound II selected from the group consisting of a quinoxaline derivative of the formula ##STR2## wherein for compound (IIa), R is Ch 3  and X is O and wherein for compound (IIb), R is H and X is S.

The present invention relates to new fungicidal active compoundcombinations comprising known 1,2,4-triazole derivatives ofphenoxyether-ketones and phenoxyether-alkanols and other knownfungicidal active compounds.

It has already been disclosed that 1,2,4-triazole derivatives ofphenoxyether-ketones and phenoxyetheralkanols, such as, for example,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one andthe corresponding butan-2-ol derivative, have a good action againstfungi which damage plants (in this context, see the German PatentSpecification No. 2,201,064 and U.S. Pat. No. 3,952,002), and inparticular the action against powdery mildew fungi should be mentioned,as well as against rust diseases, leaf spot diseases and smut diseasesin various crop plants.

The following fungicidal active compounds or active compound groups havelikewise been disclosed:

(A) Quinoxaline derivatives, such as, for example,6-methyl-quinoxaline-2,3-cycl.-dithiolcarbonate (CHINOMETHIONAT) andquinoxaline-2,3-cycl.-trithiocarbonate (CHINOTHIONAT) (in this context,see the data in R. Wegler, "Chemie der Pflanzenschutz- undSchadlingsbekampfungsmittel" (Chemistry of plant protection agents andpest-combating agents), volume 2, pages 128 and 129, Springer-Verlag,Berlin/Heidelberg/New York, 1970);

(B) Derivatives of imidazoles and triazoles, such as, for example, allyl1-(2,4-dichlorophenyl)-2-imidazol-1-yl-ethyl ether (FUNGAFLOR),2-(imidazol-1-yl-methyl)-2-phenyl-hexanenitrile (FENAPRONIL),1-cyclohexyl-2-(1,2,4-triazol-1yl)-3-hydroxy-4,4-dimethyl-pent-1-ene,1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole(PROPICONAZOL),1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl]-methyl-1H-1,2,4-triazole(ETACONAZOLE),1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-pentan-3-ol(DICLOBUTRAZOL),1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethylpentan-3-ol,1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-3-hydroxy-4,4-dimethyl-pent-1-ene,1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-3-hydroxy-4,4-dimethyl-pent-1-eneand 4-(n-butyl)-4H-1,2,4-triazole (TRIAZBUTIL) (in this context, seeDE-OS (German Published Specification) 2,429,523, DE-OS (GermanPublished Specification) 2,063,857, DE-OS (German PublishedSpecification) 2,604,047, U.S. Ser. No. 294,603 filed Aug. 20, 1981, nowpending, DE-OS (German Published Specification) 2,551,560, DE-OS (GermanPublished Specification) 2,737,489, DE-OS (German PublishedSpecification) 3,010,560 and U.S. Pat. No. 3,647,810).

(C) Derivatives of phenylureas, such as, for example,1-phenyl-3-cyclopentyl-3-(4-chlorobenzyl)-urea (PENCYCURON), see GermanPatent Specification 2,732,257;

(D) Bis-trifluoromethylimino five-membered ring compounds, such as, forexample,2-phenylimino-3-phenyl-4,5-bis(trifluoromethylimino)-thiazolidine(FLUBENZIMINE), and the compound of the formula ##STR3## (in thisconnection, see U.S. Pat. No. 3,895,020 and No. 3,787,435.

(E) Derivatives of 3-azolyl-benzo-1,2,4-triazines and-benzo-1,2,4-triazine-1-oxides, such as, for example,3-imidazolyl-7-chlorio-benzo-1,2,4-triazine-1-oxide (see U.S. Pat. No.4,239,760);

(F) Copper salts of organic compounds, such as, for example, the coppersalt of 8-hydroxyquinoline (see R. Wegler, loc. cit., page 112);

(G) Specific alkylated derivatives of methyl benzimidazole-2-carbamate,such as, for example, the methyl ester of 4-methyl- and of5-methyl-benzimidazole-2-carbamic acid (see U.S. Pat. No. 2,933,502 andU.S. Pat. No. 2,933,504 and DE-OS (German Published Specification2,217,919 (Le A 14 420)).

The activity of the abovementioned individual active compounds is notalways completely satisfactory in particular fields of use.

It has now been found that new active compound combinations comprising1,2,4-triazole derivatives of phenoxyether-ketones andphenoxyether-alkanols of the formula ##STR4## in which R¹ representsphenyl which can be optionally substituted by halogen, nitro,trifluoromethyl, alkyl having up to 6 carbon atoms, alkoxy having up to4 carbon atoms, phenyl and 4-chlorophenyl,

R² represents hydrogen, alkyl having up to 4 carbon atoms or phenyl,

R³ represents alkyl having up to 6 carbon atoms, cycloalkyl having 5 to6 carbon atoms, phenyl or 4-chlorophenyl, and

Y represents the CO group, the group ##STR5## or C(OH)₂ or CH(OH), and

(A) quinoxaline derivatives of the formula ##STR6## and/or (B)derivatives of imidazoles and triazoles of the formulae ##STR7## and/or(C) a phenylurea of the formula ##STR8## and/or (D)bis-trifluoromethylimino five-membered ring compounds of the formulae##STR9## and/or (E) a 3-azolyl-benzo-1,2,4-triazine derivative of theformula ##STR10## and/or (F) a copper complex salt of the formula##STR11## and/or (G) a derivative, alkylated in the nucleus, of methylbenzimidazole-2-carbamate of the formula ##STR12## or comprisingmixtures of (VIIIa) and (VIIIb) have a particularly high fungicidalactivity.

Surprisingly, the fungicidal action of the active compound combinationsaccording to the invention is substantially higher than the action ofthe individual components and may also be substantially higher than thesum of the individual components (synergistic effect). The addition ofactive compounds from the abovementioned groups (A), (B), (C), (D), (E),(F) and (G) to the 1,2,4-triazole derivatives of the formula Irepresents an enrichment of the art.

The general formula I gives the definition of the 1,2,4-triazolederivatives of phenoxyether-ketones and phenoxyether-alkanols to be usedfor the combination according to the invention. In this formula, R¹represents phenyl which can be optionally preferably monosubstituted totrisubstituted by fluorine, chlorine, nitro, trifluoromethyl, methyl,methoxy and phenyl. R² preferably represents hydrogen, R³ preferablyrepresents straight-chain or branched alkyl having 1 to 4 carbon atoms,phenyl and 4-chlorophenyl, and Y has the preferred meanings CO orCH(OH). The following compounds of the formula I with the substituentmeanings given in each case may be mentioned as typical examples ofparticularly preferred 1,2,4-triazole derivatives ofphenoxyether-ketones and phenoxyether-alkanols: ##STR13##

All three compounds listed, which have the common names TRIADIMEFON(Ia), TRIADIMENOL (Ib) and BITERTANOL (Ic) are generally known (in thisconnection, see the U.S. Pat. Nos. 3,912,752 and 3,952,002.

Formulae IIa and IIb represent the quinoxaline derivatives (group A)optionally to be used as components of the mixture. The compounds havingthe common names CHINOMETHIONAT (IIa) and CHINOTHIONAT (IIb) aregenerally known (see the prior art data above). Preferred mixtures arethose which contain in the first place one of the 1,2,4-triazolederivatives of phenoxyether-ketones and phenoxyether-alkanols mentionedas examples (see the data above concerning the compounds of the formulaI) and CHINOMETHIONAT (formula IIa) as the second component.

Formulae IIIa to IIIk represent the derivatives of imidazoles andtriazoles (group B) which may furthermore be used as components of themixture. The compounds are known (see the prior art data). Preferredmixtures are those which contain in the first place one of the1,2,4-triazole derivatives of the phenoxyether-ketones andphenoxyether-alkanols mentioned as examples and in the second place anactive compound of the formula IIIa (FUNGAFLOR) or IIIc(1-cyclohexyl-2-(1,2,4-triazol-1-yl)-3-hydroxy-4,4-dimethyl-pent-1-ene.

Formula IV represents the phenylurea (group C) which may furthermore beused as a component of the mixture. The compound having the common namePENCYCURON is known (see the prior art data). Preferred mixtures arethose which contain in the first place one of the 1,2,4-triazolederivatives of phenoxyether-ketones and phenoxyether-alkanols mentionedas examples and in the second place the active compound of the formulaIV.

Formulae Va and Vc represent the bis-trifluoromethylimino five-memberedring compounds (group D) which may furthermore be used as components ofthe mixture. The compounds are known (see the prior art data). Preferredmixtures are those which contain in the first place one of the1,2,4-triazole derivatives of phenoxyether-ketones andphenoxyether-alkanols mentioned as examples, and FLUBENZIMINE (formulaVa) as the second component.

Formula VI represents the 3-azolyl-benzo-1,2,4-triazine derivative(group E) which may furthermore be used as a component of the mixture.The compound is known (see the prior art data). Preferred mixtures arethose which contain in the first place one of the 1,2,4-triazolederivatives of phenoxyether-ketones and phenoxyether-alkanols mentionedas examples and in the second place the active compound of the formulaVI.

Formula VII represents the copper complex salt (group F) which mayfurthermore be used as a component of the mixture. The compound is known(see the prior art data). Preferred mixtures are those which contain inthe first place one of the 1,2,4-triazole derivatives ofphenoxyether-ketones and phenoxyether-alkanols mentioned as examples andin the second place the active compound of the formula VII.

Formulae VIIIa and VIIIb represent the derivatives of methylbenzimidazole-2-carbamate which are alkylated in the nucleus (group G)and which may furthermore be used as components of the mixture. Thecompounds are known (see the prior art data). Preferred mixtures arethose which contain in the first place one of the 1,2,4-triazolederivatives of phenoxyether-ketones and phenoxyether alkanols mentionedas examples, and the active compounds of the formulae VIIIa and VIIIb asthe second component; in this case, the second component can also bepresent as a mixture of VIIIa and VIIIb.

In addition to the mixture components of the groups (A), (B), (C), (D),(E), (F) and (G), which, in accordance with the present invention, areto be used as a mixture with the 1,2,4-triazole derivatives ofphenoxyether-ketones and phenoxyether-alkanols of the formula (I), it isalso possible to use the following components for the mixture:

Pyrimidine derivatives, such as2-dimethylamino-4-hydroxy-5-butyl-6-methyl-pyrimidine (DIMETHIRIMOL) and2-ethylamino-4-hydroxy-5-butyl-6-methyl-pyrimidine (ETHIRIMOL);

Dimethylamidosulphonates, such as2-ethylamino-5-n-butyl-6-methyl-pyrimidin-4-yl-dimethylsulphonate(BUPIRIMATE);

Morpholine derivatives, such as 4-tridecyl-2,6-dimethylmorpholine(TRIDEMORPH) and4-[3-(4-tert.-butyl-phenyl)-2-methyl-propyl]-2,6-dimethyl-morpholine(FENPROPEMORPH);

Piperazine derivatives, such asN,N'-bis-(1-formamido-2,2,2-trichloroethyl)-piperazine (TRIFORINE);

Phenylpyrimidine derivatives, such asα-(2-chlorophenyl)-α-(4-chlorophenyl)-α-(pyrimidin-5-yl)-methanol(FENARIMOL) andα-(2-chlorophenyl)-α-(4-fluorophenyl)-α-(pyrimidin-5-yl)-methanol(NUARIMOL);

Carboxylic acid anilides, such as 2-iodobenzoic acid anilide(BENODANIL), 2-methyl-5,6-dihydro-4-H-pyran-3-carboxylic acid anilide(PYRACARBOLID), 2,4,5-trimethyl-3-furanecarboxylic acid anilide(METHFUROXAM) and 2-methyl-N-[3-(1-methylethoxy)-phenyl]-benzamide (Bi2459).

Dicarboximides, such as 1,2-dimethyl-cyclopropanedicarboxylic acidN-(3,5-dichlorophenyl)-imide (PROCYMIDONE),3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione(VINCHLOZOLIN),3-(3,5-dichlorophenyl)-2,4-dioxo-1-(N-isopropyl)-imidazolidine-carboxamide(IPRODIONE), ethyl3-(3,5-dichlorophenyl)-5-methyl-2,4-dioxo-oxazolidine-5-carboxylate(CARBOZOLINE) and N-(p-fluorophenyl)-2,3-dichloromaleinimideFLUOROIMID);

Acylalanines, such as methylN-(2,6-dimethylphenyl)-N-(2-methoxy-acetyl)-alanine (METAXANINE), methylN-(2-furoyl)-N-(2,6-xylyl)-alanine (FURALAXYL),2-chloro-N-(2,6-dimethylphenyl)-N-(tetrahydro-2-oxo-3-furanyl)-acetamide(MILFURAM), methyl N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanine(BENALAXYL) and2,6-dimethyl-N-(1-methoximino-prop-2-yl)-N-methoxyacetylaniline;

Alkoxy-imino-cyano-acetamides, such asN-ethylaminocarbonyl-2-cyano-2-methoximino-acetamide (CYMOXANIL);

Alkyl phosphites, such as the aluminum salt of O-ethyl phosphite(ALUMINIUMPHOSAETHYL);

Guanidinamines, such as bis-(8-guanidino-octyl)-amine sulphate(GUAZATINE);

Cyclopropanecarboxylic acid amides, such asN-(3-chlorophenyl)-N-(tetrahydro-2-oxo-3-furanyl)-cyclopropanecarboxylicacid amide (CYPROFURAM).

The abovementioned active compounds may also be added as a furthercomponent (for example as a third component) to a mixture of a1,2,4-triazole derivative of phenoxyether-ketones andphenoxyether-alkanols and an active compound from the groups (A) to (G).

The weight ratios of the active compound groups in the active compoundcombinations can vary within relatively wide ranges. In general, 0.02 to500 parts by weight of active compound from the active compound classes(A) to (G), preferably 0.2 to 200 parts by weight of the latter,particularly preferably 1 to 50 parts by weight, are employed per partby weight of 1,2,4-triazole derivative of the formula I.

The active compound combinations according to the invention exhibit apowderful microbicidal action and can be employed in practice forcombating undesired microorganisms. The active compounds are suitablefor use as plant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compound combinations according to the invention have a verybroad action spectrum and can be used against parasitic fungi whichinfest above-ground parts of plants or which attack the plants from theground, as well as pathogens which can be transferred by seeds. Suchactive compound combinations are of particular practical importance asseed-dressing agents against phytopathogenic fungi which are transferredwith the seed or occur in the ground and infest the crop plants fromthere. These are seedling diseases, root rots, and stalk, stem, leaf,flower, fruit and seed diseases which are caused in particular byTilletia, Urocystis, Ustilago, Septoria, Typhula, Rhynchosporium,Helminthosporium and Fusarium species. Owing to the systemic action ofone component of the mixture, the plants are also protected, frequentlyeven for a relatively long time after dressing, from pathogens which canattack the various parts of the shoot, for example powdery mildew fungiand rust fungi. In addition, the active compound combinations can alsobe employed as soil-treatment agents against phytopathogenic fungi, andare active against root rots and tracheomycoses which are caused, forexample, by pathogens of the genera Pythium, Verticillium, Phialophora,Rhizoctonia, Fusarium and Thielaviopsis.

However, the active compound combinations according to the invention,when applied directly to the above-ground parts of plants, also exhibitan outstanding action against pathogens on various crop plants, such aspowdery mildew fungi (Erysiphe, Uncinula, Sphaerotheca and Podosphaeraspecies, and Leveillula taurica), rust fungi, Venturia species,Cercospora species, Alternaria species, Botrytis species, Phytophthoraspecies, Peronospora species, Pyricularia oryzae and Pelliculariasasakii.

The active compound combinations can be converted to the customaryformulations, such as solutions, emulsions, suspensions, powders, foams,pastes, granules, aerosols, natural and synthetic materials impregnatedwith active compound, very fine capsules in polymeric substances and incoating compositions for seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans, fumigatingcoils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl napthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellant, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable; for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules and latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate can be used in theformulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and tin.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can bepresent in the formulations or in the various use forms as a mixturewith other known active compounds, such as fungicides, bactericides,insecticides, acaricides, nematicides, herbicides, bird repellants,growth factors, plant nutrients and agents for improving soil structure.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, emulsions, suspensions, powders, pastesand granules. They are used in the customary manner, for example bywatering, immersion, spraying, atomizing, misting, vaporizing,injecting, forming a slurry, brushing on, dusting, scattering, drydressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.0001 to0.1% by weight, preferably 0.0001 to 0.02%, are required at the place ofaction.

The use examples which follow serve for illustration. The activecompounds which, for example, are to be used in active compoundcombinations according to the invention are listed in the followinglist:

    ______________________________________                                        Active                                                                        com-                                                                          pound For-                                                                    No.   mula    Common name     Literature                                      ______________________________________                                         1    Ia      TRIADIMEFON     German Patent                                                                 Specification                                                                 2,201,063                                                                     U.S. Patent                                                                   Specification                                                                 3,912,752                                        2    Ib      TRIADIMENOL     German Patent                                                                 Specifica-                                                                    2,324,010                                                                     U.S. Patent                                                                   Specification                                                                 3,952,002                                        3    Ic      BITERTANOL      as in the case of                                                             compound 2                                       4    IIa     CHINOMETHIONAT  R. Wegler (loc. cit.)                                                         vol. 2, page 128                                 5    IIb     CHINOTHIONAT    R. Wegler (loc. cit.)                                                         vol. 2, page 129                                 6    IIIc    FUNGAFLOR       DE-OS (German                                                                 Published                                                                     Specification)                                                                2,063,857                                                                     U.S. Patent                                                                   Specification                                                                 3,658,813                                        7    IIIb    FENAPRONIL      DE-OS (German                                                                 Published                                                                     Specification)                                                                2,604,047                                                                     French Patent                                                                 Specification                                                                 2,300,081                                        8    IIIc                    DE-OS (German                                                                 Published                                                                     Specification)                                                                2,906,061                                                                     U.S. Specification                                                            S.N. 294,603 filed                                                            8/20/81, now pending                             9    IIId                    DE-OS (German                                                                 Published                                                                     Specification)                                                                3,010,560                                                                     British Patent                                                                Specification                                                                 2,046,260                                       10    IIIe                    as for compound 9                               11    IIIf    DICLOBUTRAZOL   DE-OS (German                                                                 Published                                                                     Specification)                                                                2,737,489                                                                     French Patent                                                                 Specification                                                                 2,362,133                                       12    IIIg                    as in the case of                                                             compound 11                                     13    IIIh    PROPICONAZOL    German Patent                                                 (proposed)      Specification                                                                 2,551,560                                                                     British Patent                                                                Specification                                                                 1,522,657                                       14    IIIi    ETACONAZOLE     as in the case of                                             (proposed)      compound 13                                     15    IIIk    TRIAZBUTIL      R. Wegler (loc. cit.),                                                        vol. 4, page 210                                                              U.S. Patent                                                                   Specification                                                                 3,647,810                                       16    IV      PENCYCURON      German Patent                                                                 Specification                                                                 2,732,257                                                                     U.S. Patent                                                                   Specification                                                                 4,127,673                                       17    Va      FLUBENZIMINE    German Patent                                                                 Specification                                                                 2,082,348                                                                     U.S. Patent                                                                   Specification                                                                 3,895,020                                       18    Vb                      DE-OS (German                                                                 Published                                                                     Specification)                                                                2,062,346                                                                     U.S. Patent                                                                   Specification                                                                 3,787,435                                                                     U.S. Patent                                                                   Specification                                                                 3,934,019                                       19    VI                      DE-OS (German                                                                 Published                                                                     Specification)                                                                2,802,488                                                                     U.S. Patent                                                                   Specification                                                                 4,239,760                                       20    VII     OXINE-COPPER    R. Wegler, loc. cit.,                                                         page 112                                        21    VIIIa                   U.S. Patent                                                                   Specification                                                                 2,933,502                                                                     U.S. Patent                                                                   Specification                                                                 2,933,504                                       22    VIIIb                   DE-OS (German                                                                 Published                                                                     Specification)                                                                2,217,919                                                                     U.S. Patent                                                                   Specification                                                                 3,993,846                                       ______________________________________                                    

EXAMPLE A

Erysiphe test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

                  TABLE A                                                         ______________________________________                                        Erysiphe test (barley)/protective                                                                          Disease in-                                                      Active compound                                                                            festation in                                                     concentration in                                                                           % of the un-                                     Active          the spray liquor                                                                           treated con-                                     compound        in % by weight                                                                             trol                                             ______________________________________                                        1 (TRIADIMEFON) 0.00025      25.0                                             (known)         0.0001       66.3                                             4 (CHINOMETHIONAT)                                                                            0.00025      100                                              (known)         0.0001       100                                              Mixture of 1 and 4                                                                              0.00025 +  12.5                                             (Mixing ratio 1:1)                                                                            0.00025                                                       Mixture 1 and 4  0.0001 +    25.0                                             (Mixing ratio 1:1)                                                                            0.0001                                                        ______________________________________                                    

EXAMPLE B

Sphaerotheca test (cucumber)/protective

To test for protective activity, young plants are sprayed with acommercial formulation until dripping wet. After the spray coating hasdried on, the plants are dusted with conidia of the fungus Sphaerothecafuliginea.

The plants are then placed in a greenhouse at 23 to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

                  TABLE B                                                         ______________________________________                                        Sphaerotheca test (cucumber)/protective                                       Active          Active compound                                                                             Infestation                                     compound        concentration in %                                            ______________________________________                                        1 (TRIADIMEFON) 0.00006%      50                                              (known)                                                                       4 (CHINOMETHIONAT)                                                                            0.00006%      96                                              (known)                                                                       Mixture of 1 and 4                                                                              0.00006% +  38                                              (Mixing ratio 1:1)                                                                            0.00006%                                                      ______________________________________                                    

EXAMPLE C

Drechslera graminea test (barley)/seed treatment (syn. Helminthosporiumgramineum)

The active compounds are used as dry dressings. There are produced byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the infected seed is shaken with the dressing ina closed glass flask for 3 minutes.

The seed is embedded in sieved, moist standard soil and is exposed to atemperature of 4° C. in closed Petri dishes in a refrigerator for 10days. Germination of the barley, and possibly also of the fungus spores,is thereby initiated. 2 batches of 50 grains of the pregerminated barleyare subsequently sown 3 cm deep in standard soil and are cultivated in agreenhouse at a temperature of about 18° C., in seedboxes which areexposed to light for 15 hours daily.

About 3 weeks after sowing, the plants are evaluated for symptoms ofstripe disease.

                  TABLE C                                                         ______________________________________                                        Drechslera graminea test (barley)/seed treatment                              (syn. Helminthosporium gramineum)                                                                          Diseased                                                            Amount of plants                                                              active    in % of                                                             compound  the total                                                           applied   plants                                                              in mg/kg  which have                                       Active compound    of seed   emerged                                          ______________________________________                                        not dressed        --        28.8                                             2 (TRIADIMENOL)    200       12.3                                             (known)                                                                       19 (Compound of the formula                                                                      10        4.9                                              (VI))                                                                         (known)                                                                       6 (FUNGAFLOR)      10        8.3                                              (known)                                                                       Mixture of 2 and 19                                                                                200 +   0.0                                              (Mixing ratio 1:0.05)                                                                            10                                                         Mixture of 2 and 6   200 +   0.0                                              (Mixing ratio 1:0.05                                                                             10                                                         ______________________________________                                    

EXAMPLE D

Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabin at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

                  TABLE D                                                         ______________________________________                                        Leptosphaeria nodorum test (wheat)/protective                                                              Disease in-                                                     Active compound                                                                             festation in                                                    concentration in                                                                            % of the un-                                     Active         the spray liquor                                                                            treated con-                                     compound       in % by weight                                                                              trol                                             ______________________________________                                        1 (TRIADIMEFON)                                                                              0.01          100                                              (known)                                                                       17 (FLUBENZIMINE)                                                                            0.01          50                                               (known)                                                                       21 (Compound of the                                                                          0.0025        82.5                                             formula (VIIIa))                                                                             0.0025        82.5                                             (known)                                                                       Mixture of 1 and 17                                                                          .sup. 0.01 +  25.0                                             (Mixing ratio 1:1)                                                                           0.01                                                           Mixture of 1 and 21                                                                          .sup. 0.01 +  50.0                                             (Mixing ratio 1:0.25)                                                                        0.0025                                                         ______________________________________                                    

EXAMPLE E

Pyrenophora teres test (barley)/protective/

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofPyrenophora teres. The plants remain in an incubation cabinet at 20° C.and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

                  TABLE E                                                         ______________________________________                                        Pyrenophora teres test (barley)/protective                                                                Disease in-                                                      Active compound                                                                            festation in                                                     concentration in                                                                           % of the un-                                      Active         the spray liquor                                                                           treated con-                                      compound       in % by weight                                                                             trol                                              ______________________________________                                        1 (TRIADIMEFON)                                                                               0.005       100                                               (known)                                                                       8 (Compound of the                                                                           0.01         100                                               formula (IIIc))                                                               (known)                                                                       Mixture of 1 and 8                                                                              0.005 +   21.3                                              (Mixing ratio 1:2)                                                                           0.01                                                           ______________________________________                                    

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A fungicidal composition comprising afungicidally effective amount of compound I selected from the groupconsisting of ##STR14## and an approximately equal weight of compound IIselected from the group consisting of a quinoxaline derivative of theformula ##STR15## wherein for compound (IIa), R is --CH₃ and X is O andwherein for compound (IIb), R is H and X is S.
 2. A fungicidalcomposition according to claim 1, wherein I is ##STR16## and compound IIis (IIa).
 3. A process for combating fungi which comprises applying tofungi or their habitat a fungicidally effective amount of a compositionaccording to claim
 1. 4. A process for combating fungi which comprisesapplying to fungi or their habitat a fungicidally effective amount of acomposition according to claim 2.